Transition metal ammine complexes as activators for peroxide compounds

ABSTRACT

A method of oxidizing, washing, cleaning, or disinfecting a soiled article is provided wherein a peroxygen compound is activated by an effective amount of a complex of the formula (I): 
     
       
         [M (NH 3 ) 6−x (L) x ]A n   (I) 
       
     
     wherein M is iron, copper, or ruthenium, x is a number of 0 to 5, L is a ligand, and A is a salt-forming anion. Also provided are compositions comprising 0.0025% to 0.25% by weight of the complex (I).

BACKGROUND OF THE INVENTION

This invention relates to the use of certain oligoammine complexes oftransition metals as activators or catalysts for peroxygen compounds,more particularly for bleaching colored stains in the washing oftextiles, and to detergents, cleaners and disinfectants containing suchbleach activators or bleach catalysts.

Inorganic peroxygen compounds, more particularly hydrogen peroxide, andsolid peroxygen compounds which dissolve in water with elimination ofhydrogen peroxide, such as sodium perborate and sodium carbonateperhydrate, have long been used as oxidizing agents for disinfecting andbleaching purposes. In dilute solutions, the oxidizing effect of thesesubstances depends to a large extent on the temperature. For example,with H₂O₂ or perborate in alkaline bleaching liquors, sufficiently rapidbleaching of soiled textiles is only achieved at temperatures aboveabout 80° C. At lower temperatures, the oxidizing effect of theinorganic peroxygen compounds can be improved by addition of so-calledbleach activators for which numerous proposals, above all from theclasses of N- or O-acyl compounds, for example polyacylatedalkylenediamines, more particularly tetraacetyl ethylenediamine,acylated glycolurils, more particularly tetraacetyl glycoluril,N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles,diketopiperazines, sulfuryl amides and cyanurates, also carboxylicanhydrides, more particularly phthalic anhydride, carboxylic acidesters, more particularly sodium nonanoyloxybenzenesulfonate, sodiumisononanoyloxy-benzenesulfonate and acylated sugar derivatives, such aspentaacetyl glucose, can be found in the literature. By adding thesesubstances, the bleaching effect of aqueous peroxide liquors can beincreased to such an extent that substantially the same effects areobtained at temperatures of only 60° C. as are obtained with theperoxide liquor alone at 95° C.

In the search for energy-saving washing and bleaching processes,operating temperatures well below 60° C. and, more particularly, below45° C. down to the temperature of cold water have acquired increasingsignificance in recent years.

At these low temperatures, there is generally a discernible reduction inthe effect of known activator compounds. Accordingly, there has been noshortage of attempts to develop more effective activators for thistemperature range although the results achieved thus far have not beenconvincing. A starting point in this connection is the use of thetransition metal salts and complexes proposed, for example, in Europeanpatent applications EP 392 592, EP 443 651, EP 458 397, EP 544 490 or EP549 271 as so-called bleach catalysts. In their case, the highreactivity of the oxidizing intermediates formed from them and theperoxygen compound is presumably responsible for the risk ofdiscoloration of colored textiles and, in extreme cases, oxidativetextile damage. In European patent application EP 272 030, cobalt(III)complexes with ammonia ligands which may additionally contain othermono-, bi-, tri- and/or tetradentate ligands are described as activatorsfor H₂O₂. European patent application EP 630 964 describes certainmanganese complexes which do not have a pronounced effect in boostingthe bleaching action of peroxygen compounds and which do not decolordyed textile fibers although they are capable of bleaching soil or dyedetached from fibers in wash liquors. German patent application DE 44 16438 describes manganese, copper and cobalt complexes which can carryligands from a number of groups of compounds and which are said to beused as bleaching and oxidation catalysts.

The problem addressed by the present invention was to improve theoxidizing and bleaching effect of inorganic peroxygen compounds at lowtemperatures below 80° C. and, more particularly, in the range fromabout 15° C. to 45° C.

It has now been found that certain transition metal complexes containingat least one ammonia molecule as ligand have a distinct effect as bleachcatalysts.

DESCRIPTION OF THE INVENTION

The present invention relates to the use of complex compoundscorresponding to general formula I:

[M(NH₃)_(6−x)(L)_(x)]A_(n)  (I)

where M is a transition metal selected from cobalt, iron, copper andruthenium, L is a ligand selected from the group consisting of water,hydroxide, chlorate, perchlorate, (NO₂)⁻, carbonate, hydrogen carbonate,nitrate, acetate and thiocyanate, x is a number of 0 to 5, A is asalt-forming anion and n—which may even be 0—is a number with such avalue that the compound of formula (I) has no charge, as activators forperoxygen compounds, particularly inorganic peroxygen compounds, inoxidizing, washing, cleaning or disinfecting solutions.

In the present case, an (NO₂)⁻group is a nitro ligand which is attachedto the transition metal by the nitrogen atom or a nitrito ligand whichis attached to the transition metal by an oxygen atom. The (NO₂)⁻groupmay also be attached to a transition metal M to form a chelate

It may also bridge two transition metal atoms asymmetrically:

The above-mentioned transition metals in the bleach catalysts to be usedin accordance with the invention are preferably present with oxidationnumbers of +2, +3 or +4. Complexes with transition metal central atomshaving the oxidation number +3 are preferably used. Preferred complexesinclude those with cobalt as central atom.

Besides the ammonia ligands, the transition metal complexes to be usedin accordance with the invention may contain other inorganic ligands ofgenerally simple structure (L in formula I), more particularly mono- orpolyvalent anionic ligands, providing at least one ammonia molecule ispresent as ligand in the complex. Examples of such other ligands arenitrate, acetate, thiocyanate, chlorate and perchlorate. The anionicligands are intended to provide for charge equalization between thetransition metal central atom and the ligand system. Oxo ligands, peroxoligands and imino ligands may also be present in addition to or insteadof the ligands L. These ligands may also have a bridging effect so thatpolynuclear complexes are formed. These complexes contain at least oneammonia ligand and preferably at least one (NO₂)− group per transitionmetal atom. In the case of bridged binuclear complexes, the two metalatoms in the complex do not have to be the same. Binuclear complexes inwhich the two transition metal central atoms have different oxidationnumbers may be used.

In the absence of anionic ligands or if the presence of anionic ligandsdoes not lead to charge equalization in the complex, the compounds to beused in accordance with the invention contain anionic counterions whichneutralize the cationic complex. These anionic counterions include inparticular nitrate, hydroxide, hexafluorophosphate, sulfate, chlorate,perchlorate, halides, such as chloride, fluoride, iodide and bromide, orthe anions of carboxylic acids, such as formate, acetate, benzoate orcitrate. These anionic counterions are present in the compounds offormula I in such a number (n in formula I) that—in terms of size—thesum of the product of their number with their charge and the product ofthe number of anionic ligands (L in formula I) with their charge isexactly as large, but with a negative sign, as the charge of thetransition metal central atom (M in formula I).

In cases where L is a bidentate ligand, for example the carbonatoligand, as mentioned above, optionally the (NO₂)⁻ ligand or the nitratoligand, which occupies two bond sites of the transition metal centralatom in a mononuclear complex compound, formula (I) can only analogouslyreproduce the structure of the complex. Complex compounds such as theseare more clearly represented by general formula (II):

[M(NH₃)_(6−x−2y)L_(x)(L²)_(y)]A_(n)  (II)

where M, A, n and x are as defined above, L is a ligand attached via acoordination site and L² is the ligand attached via two coordinationsites and y is a number of 0 to 2, with the proviso that x+2y is at most5.

Preferred bleach catalysts according to the invention includenitropentammine cobalt(III) chloride, nitritopentammine cobalt(III)chloride, nitratopentammine cobalt(III) chloride, tetramminecarbonato-cobalt(III) chloride, tetrammine carbonato-cobalt(III)hydrogen carbonate and tetrammine carbonato-cobalt(III) nitrate.

A transition metal bleach catalyst such as this is preferably used forbleaching colored stains in the washing of textiles, particularly in awater-based surfactant-containing liquor. The expression “bleaching ofcolored stains” is meant to be interpreted in its broadest sense andencompasses both the bleaching of soil present on the textiles, thebleaching of soil detached from the textiles and present in the washliquor and the oxidative destruction of textile dyes present in the washliquor—which are detached from textiles under the washingconditions—before they can be absorbed by differently colored textiles.

The present invention also relates to detergents, cleaners anddisinfectants containing one of the above-mentioned transition metalbleach catalysts and to a process for activating peroxygen compoundsusing this bleach catalyst.

In the process according to the invention and in the uses according tothe invention, the bleach catalyst may be used as an activator anywherewhere a particular increase in the oxidizing effect of the peroxygencompounds at low temperatures is required, for example in the bleachingof textiles or hair, in the oxidation of organic or inorganicintermediates and in disinfection.

The use according to the invention essentially comprises creatingconditions under which the peroxygen compound and the bleach catalystcan react with one another with a view to obtaining products with astronger oxidizing effect. Such conditions prevail in particular whenboth reactants meet in an aqueous solution. This can be achieved byseparately adding the peroxygen compound and the bleach catalyst to asolution optionally containing a detergent or cleaner. In oneparticularly advantageous embodiment, however, the process according tothe invention is carried out using a detergent, cleaner or disinfectantaccording to the invention which contains the bleach catalyst andoptionally a peroxidic oxidizing agent. The peroxygen compound may evenbe separately added to the solution as such or preferably in the form ofan aqueous solution or suspension in cases where a peroxygen-freeformulation is used.

The conditions can be widely varied according to the applicationenvisaged. Thus, besides purely aqueous solutions, mixtures of water andsuitable organic solvents may serve as the reaction medium. Thequantities of peroxygen compounds used are generally selected so thatthe solutions contain between 10 ppm and 10% of available oxygen andpreferably between 50 and 5000 ppm of available oxygen. The quantity ofbleach-catalyzing transition metal compound used is also determined bythe particular application envisaged. Depending on the required degreeof activation, the transition metal compound is used in a quantity of0.00001 mole to 0.025 mole and preferably in a quantity of 0.0001 moleto 0.002 mole per mole of peroxygen compound, although quantities aboveand below these limits may be used in special cases.

A detergent, cleaner or disinfectant according to the inventionpreferably contains 0.0025% by weight to 0.25% by weight and, morepreferably, 0.01% by weight to 0.1% by weight of the transition metalbleach catalyst corresponding to formula I in addition to typicalingredients compatible with the bleach catalyst. The bleach catalyst maybe adsorbed onto supports and/or encapsulated in shell-formingsubstances by methods known in principle.

In addition to the bleach catalyst used in accordance with theinvention, the detergents, cleaners and disinfectants according to theinvention, which may be present in the form of—in particular—powder—formsolids, in the form of post-compacted particles or in the form ofhomogeneous solutions or suspensions, may in principle contain any knowningredients typically encountered in such formulations. In particular,the detergents and cleaners according to the invention may containbuilders, surfactants, organic and/or inorganic peroxygen compounds,water-miscible organic solvents, enzymes, sequestering agents,electrolytes, pH regulators and other auxiliaries, such as opticalbrighteners, redeposition inhibitors, dye transfer inhibitors, foamregulators, additional peroxygen activators, dyes and perfumes.

In addition to the ingredients mentioned thus far, a disinfectantaccording to the invention may contain typical antimicrobial agents toenhance its disinfecting effect on special germs. Antimicrobialadditives of the type in question are present in the disinfectantsaccording to the invention in quantities of preferably not more than 10%by weight and, more preferably, in quantities of 0.1% by weight to 5% byweight.

Standard transition metal complexes and/or—particularly in combinationwith inorganic peroxygen compounds—conventional bleach activators, i.e.compounds which form optionally substituted perbenzoic acid and/oraliphatic peroxocarboxylic acids containing 1 to 10 and moreparticularly 2 to 4 carbon atoms under perhydrolysis conditions, may beused in addition to the transition metal bleach catalysts correspondingto formula I which contain at least one ammonia molecule as ligand.Suitable conventional bleach activators are the typical bleachactivators mentioned at the beginning which contain O- and/or N-acylgroups with the number of carbon atoms mentioned and/or optionallysubstituted benzoyl groups. Preferred conventional bleach activators arepolyacylated alkylenediamines, more particularly tetraacetylethylenediamine (TAED), acylated glycolurils, more particularlytetraacetyl glycoluril (TAGU), acylated triazine derivatives, moreparticularly 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT),acylated phenol sulfonates, more particularly nonanoyl orisononanoyloxybenzenesulfonate, acylated polyhydric alcohols, moreparticularly triacetin, ethylene glycol diacetate and2,5-diacetoxy-2,5-dihydrofuran, and acetylated sorbitol and mannitol,acylated sugar derivatives, more particularly pentaacetyl glucose (PAG),pentaacetyl fructose, tetaacetyl xylose and octaacetyl lactose andacetylated, optionally N-alkylated glucamine and gluconolactone. Thecombinations of conventional bleach activators known from German patentapplication DE 44 43 177 may also be used.

The formulations according to the invention may contain one or moresurfactants, more particularly anionic surfactants, nonionic surfactantsand mixtures thereof. Suitable nonionic surfactants are, in particular,alkyl glycosides and ethoxylation and/or propoxylation products of alkylglycosides or linear or branched alcohols containing 12 to 18 carbonatoms in the alkyl group and 3 to 20 and preferably 4 to 10 alkyl ethergroups. Corresponding ethoxylation and/or propoxylation products ofN-alkylamines, vicinal diols, fatty acid esters and fatty acid amidescorresponding to the long-chain alcohol derivatives in regard to thealkyl moiety and of alkylphenols containing 5 to 12 carbon atoms in thealkyl group may also be used.

Suitable anionic surfactants are, in particular, soaps and those whichcontain sulfate or sulfonate groups preferably having alkali metal ionsas cations. Preferred soaps are the alkali metal salts of saturated orunsaturated fatty acids containing 12 to 18 carbon atoms. Fatty acidssuch as these need not even be completely neutralized for use inaccordance with the invention. Suitable surfactants of the sulfate typeinclude salts of sulfuric acid semi-esters of fatty alcohols containing12 to 18 carbon atoms and sulfation products of the nonionic surfactantsmentioned with a low degree of ethoxylation. Suitable surfactants of thesulfonate type include linear alkylbenzenesulfonates containing 9 to 14carbon atoms in the alkyl moiety, alkanesulfonates containing 12 to 18carbon atoms and olefin sulfonates containing 12 to 18 carbon atoms,which are formed in the reaction of corresponding monoolefins withsulfur trioxide, and also α-sulfofatty acid esters which are formed inthe sulfonation of fatty acid methyl or ethyl esters.

Surfactants such as these are present in the cleaners or detergentsaccording to the invention in quantities of, preferably, 5% by weight to50% by weight and, more preferably, 8% by weight to 30% by weight whilethe disinfectants according to the invention and machine dishwashingdetergents according to the invention preferably contain 0.1% by weightto 20% by weight and, more preferably, 0.2% by weight to 5% by weight ofsurfactants.

Particularly suitable peroxygen compounds are organic peracids orperacidic salts of organic acids, such as phthalimidopercaproic acid,perbenzoic acid or salts of diperdodecane diacid, hydrogen peroxide andinorganic salts which give off hydrogen peroxide under the cleaningconditions, such as perborate, percarbonate and/or persilicate. If solidper compounds are to be used, they may be employed in the form ofpowders or granules which may even be coated in known manner. Theperoxygen compounds may be added to the wash or cleaning liquor eitheras such or in the form of formulations containing them which, inprinciple, may comprise all the usual ingredients of detergents,cleaners or disinfectants. In one particularly preferred embodiment,alkali metal percarbonate, alkali metal perborate monohydrate orhydrogen peroxide is used in the form of an aqueous solution containing3% by weight to 10% by weight of hydrogen peroxide. If a detergent orcleaner according to the invention contains peroxygen compounds, theperoxygen compounds are present in quantities of preferably up to 50% byweight and, more preferably, in quantities of 5% by weight to 30% byweight whereas the disinfectants according to the invention preferablycontain from 0.5% by weight to 40% by weight and, more preferably, from5% by weight to 20% by weight of peroxygen compounds.

A formulation according to the invention preferably contains at leastone water-soluble and/or water-insoluble, organic and/or inorganicbuilder. Water-soluble organic builders include polycarboxylic acids,more particularly citric acid and sugar acids, monomeric and polymericaminopolycarboxylic acids, more particularly methyl glycine diaceticacid, nitrilotriacetic acid and ethylenediamine tetraacetic acid, andpolyaspartic acid, polyphosphonic acids, more particularlyaminotris-(methylenephosphonic acid), ethylenediaminetetrakis(methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonicacid, polymeric hydroxy compounds, such as dextrin, and polymeric(poly)carboxylic acids, more particularly the polycarboxylatesobtainable by oxidation of polysaccharides according to Internationalpatent application WO 93/16110, polymeric acrylic acids, methacrylicacids, maleic acids and copolymers thereof which may also contain smallamounts of polymerizable substances with no carboxylic acidfunctionality in copolymerized form. The relative molecular weight ofthe homopolymers of unsaturated carboxylic acids is generally in therange from 5,000 to 200,000 while the relative molecular weight of thecopolymers is between 2,000 and 200,000 and preferably between 50,000and 120,000, based on free acid. A particularly preferred acrylicacid/maleic acid copolymer has a relative molecular weight of 50,000 to100,000. Suitable, albeit less preferred, compounds of this class arecopolymers of acrylic acid or methacrylic acid with vinyl ethers, suchas vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene,in which the acid makes up at least 50% by weight of the copolymer.Other suitable water-soluble organic builders are terpolymers whichcontain two unsaturated acids and/or salts thereof as monomers and vinylalcohol and/or an esterified vinyl alcohol or a carbohydrate as thethird monomer. The first acidic monomer or its salt is derived from amonoethylenically unsaturated C₃₋₈ carboxylic acid and preferably from aC₃₋₄ monocarboxylic acid, more particularly from (meth)acrylic acid. Thesecond acidic monomer or its salt may be a derivative of a C₄₋₈dicarboxylic acid, maleic acid being particularly preferred, and/or aderivative of an allylsulfonic acid substituted in the 2-position by analkyl or aryl group. Polymers such as these may be produced inparticular by the processes described in German patent DE 42 21 381 andin German patent application DE 43 00 772 and generally have a relativemolecular weight in the range from 1,000 to 200,000. Other preferredcopolymers are the copolymers which are described in German patentapplications DE 43 03 320 and DE 44 17 734 and which preferably containacrolein and acrylic acid/acrylic acid salts or vinyl acetate asmonomers. The organic builders may be used in the form of aqueoussolutions, preferably 30 to 50% by weight aqueous solutions,particularly for the production of liquid formulations. All the acidsmentioned are generally used in the form of their water-soluble salts,more particularly their alkali metal salts.

If desired, organic builders of the type in question may be present inquantities of up to 40% by weight, more particularly in quantities of upto 25% by weight and preferably in quantities of 1% by weight to 8% byweight. Quantities near the upper limit mentioned are preferably used inpaste-form or liquid, more particularly water-containing, formulationsaccording to the invention.

Particularly suitable water-soluble inorganic builders arepolyphosphates, preferably sodium triphosphate. Particularly suitablewater-insoluble, water-dispersible inorganic builders are crystalline oramorphous alkali metal alumosilicates used in quantities of up to 50% byweight and preferably in quantities of not more than 40% by weight and,in liquid formulations, particularly in quantities of 1% by weight to 5%by weight. Of these inorganic builders, detergent-range crystallinesodium alumosilicates, more particularly zeolite A, P and optionally X,are preferred. Quantities approaching the upper limit mentioned arepreferably used in solid particulate formulations. Suitablealumosilicates contain in particular no particles larger than 30 μm insize, at least 80% by weight preferably consisting of particles below 10μm in size. Their calcium binding capacity, which may be determined inaccordance with German patent DE 24 12 837, is generally in the rangefrom 100 to 200 mg CaO per gram.

Suitable substitutes or partial substitutes for the alumosilicatementioned are crystalline alkali metal silicates which may be presenteither on their own or in the form of a mixture with amorphoussilicates. The alkali metal silicates suitable for use as builders inthe formulations according to the invention preferably have a molarratio of alkali metal oxide to SiO₂ of less than 0.95:1 and, moreparticularly, from 1:1.1 to 1:12 and may be present in amorphous orcrystalline form. Preferred alkali metal silicates are the sodiumsilicates, more particularly the amorphous sodium silicates, with amolar Na₂O:SiO₂ ratio of 1:2 to 1:2.8. Those with a molar Na₂O:SiO₂ratio of 1:1.9 to 1:2.8 may be produced by the process according toEuropean patent application EP 0 425 427. Preferred crystallinesilicates, which may be present either on their own or in the form of amixture with amorphous silicates, are crystalline layer silicates withthe general formula Na₂Si_(x)O_(2x+1)yH₂O, where x—the so-calledmodulus—is a number of 1.9 to 4 and y is a number of 0 to 20, preferredvalues for x being 2, 3 or 4. Crystalline layer silicates whichcorrespond to this general formula are described, for example, inEuropean patent application EP 0 164 514. Preferred crystalline layersilicates are those in which x in the general formula mentioned assumesa value of 2 or 3. Both β- and δ-sodium disilicates (Na₂Si₂O₅yH₂O) areparticularly preferred, β-sodium disilicate being obtainable, forexample, by the process described in International patent application WO91/08171. δ-Sodium silicates with a modulus of 1.9 to 3.2 may beproduced in accordance with Japanese patent applications JP 04/238 809or JP 04/260 610. Substantially water-free crystalline alkali metalsilicates corresponding to the above general formula, in which x is anumber of 1.9 to 2.1, obtainable from amorphous alkali metal silicatesas described in European patent applications EP 0 548 599, EP 0 502 325and EP 0 425 428, may also be used in the formulations according to theinvention. Another preferred embodiment of formulations according to theinvention uses a crystalline sodium layer silicate with a modulus of 2to 3 obtainable from sand and soda by the process according to Europeanpatent application EP 0 436 835. Crystalline sodium silicates with amodulus of 1.9 to 3.5 obtainable by the processes according to Europeanpatents EP 0 164 552 and/or EP 0 294 753 are used in another preferredembodiment of the formulations according to the invention. If alkalimetal alumosilicate, particularly zeolite, is present as an additionalbuilder, the ratio by weight of alumosilicate to silicate, expressed aswater-free active substances, is preferably from 1:10 to 10:1. Informulations containing both amorphous and crystalline alkali metalsilicates, the ratio by weight of amorphous alkali metal silicate tocrystalline alkali metal silicate is preferably 1:2 to 2:1 and, morepreferably, 1:1 to 2:1.

Builders are present in the detergents or cleaners according to theinvention in quantities of, preferably, up to 60% by weight and, morepreferably, from 5% by weight to 40% by weight while the disinfectantsaccording to the invention are preferably free from the builders whichonly complex the components of water hardness and contain preferably nomore than 20% by weight and, more preferably, from 0.1% by weight to 5%by weight of heavy metal complexing agents, preferably from the groupconsisting of aminopolycarboxylic acids, aminopolyphosphonic acids andhydroxypolyphosphonic acids and water-soluble salts and mixturesthereof.

Enzymes suitable for use in the detergents/cleaners/disinfectants areenzymes from the class of proteases, lipases, cutinases, amylases,pullulanases, hemicellulases, cellulases, oxidases and peroxidases andmixtures thereof. Particularly suitable enzymes are those obtained fromfungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis,Streptomyces griseus, Humicola lanuginosa, Humicola insolens,Pseudomonas pseudoalcaligenes or Pseudomonas cepacia. As described forexample in International patent applications WO 92/11347 or WO 94/23005,the enzymes optionally used may be adsorbed onto supports and/orencapsulated in shell-forming substances to protect them againstpremature inactivation. They are added to the detergents, cleaners anddisinfectants according to the invention in quantities of preferably notmore than 5% by weight and, more preferably between 0.2% by weight and2% by weight.

Organic solvents suitable for use in the formulations according to theinvention, particularly where they are present in liquid or paste-likeform, include alcohols containing 1 to 4 carbon atoms, more particularlymethanol, ethanol, isopropanol and tert.butanol, diols containing 2 to 4carbon atoms, more particularly ethylene glycol and propylene glycol,and mixtures thereof and the ethers derived from compounds belonging tothe classes mentioned above. Water-miscible solvents such as these arepresent in the detergents, cleaners and disinfectants according to theinvention in quantities of preferably not more than 30% by weight and,more preferably, in quantities of 6% by weight to 20% by weight.

To establish a desired pH value which is not automatically adjusted bythe mixture of the other components, the formulations according to theinvention may contain system-compatible and ecologically compatibleacids, more particularly citric acid, acetic acid, tartaric acid, malicacid, lactic acid, glycolic acid, succinic acid, glutaric acid and/oradipic acid, and mineral acids, more particularly sulfuric acid, orbases, more particularly ammonium or alkali metal hydroxides. pHregulators such as these are present in the formulations according tothe invention in quantities of preferably not more than 20% by weightand, more preferably, between 1.2% by weight and 17% by weight.

The production of the solid formulations according to the invention doesnot involve any difficulties and may be carried out by methods known inprinciple, for example by spray drying or granulation, the peroxygencompound and bleach catalyst optionally being added later. To produceformulations according to the invention with high bulk density, moreparticularly in the range from 650 g/l to 950 g/l, a process comprisingan extrusion step known from European patent EP 486 592 is preferablyapplied. Detergents, cleaners or disinfectants according to theinvention in the form of aqueous solutions or solutions containing othertypical solvents are produced with particular advantage simply by mixingthe ingredients which may be introduced into an automatic mixer eitheras such or in the form of a solution. In one preferred embodiment ofmachine dishwashing formulations, the formulations are produced in theform of tablets by the processes disclosed in European patents EP 0 579659 and EP 0 591 282.

EXAMPLES

A tea-stained cloth of white cotton was washed for 20 minutes at 30° C.in a Launderometer using a bleach-activator-free detergent B1 containing16% by weight of sodium perborate monohydrate. After rinsing and drying,the reflectance (measurement wavelength 460 nm) of the apparently cleantest cloth was photometrically determined. In addition, a detergent B2containing 6% by weight of TAED and 94% by weight of B1 was tested inthe same dosage under the same conditions. The value obtained using adetergent M1 which contained B1, 3% by weight of TAED and the complexnitritopentammine cobalt(III) chloride in a concentration of 50 ppm,based on cobalt, was clearly superior to the values obtained in thecomparison tests (Table 1).

TABLE 1 Reflectance values [%] Detergent Reflectance B1 58.0 B2 63.6 M165.1

It can be seen that a significantly better bleaching effect can beobtained through the use according to the invention (M1) than by theconventional bleach activator TAED in a far higher concentration (B2).

What is claimed is:
 1. A method of oxidizing, washing, cleaning, ordisinfecting a soiled article wherein a peroxygen compound in anoxidizing, washing, or cleaning solution serving as a reaction medium,said peroxygen compound being in an amount selected to provide saidreaction medium with 10 ppm to 10% of available oxygen, is activated by0.00001 to 0.025 moles per mole of said peroxvgen compound of a complexof the formula (I): [M(NH₃)_(6−x)(L)_(x)]A_(n)  (I) wherein M is, iron,copper, or ruthenium, L is water, hydroxide, chlorate, perchlorate,(NO₂)⁻, carbonate, hydrogen carbonate, nitrate, acetate, or thiocyanate,x is a number of 0 to 5, A is a salt-forming anion, and n is a numbersuch that complex (I) is has no charge.
 2. A method according to claim 1comprising bleaching colored stains on a textile article.
 3. A methodaccording to claim 1, wherein M has an oxidation number of +2, +3, or+4.
 4. A method according to claim 1, wherein A is a halide or an anionof a carboxylic acid.
 5. A method according to claim 4, wherein A ischloride.
 6. A method according to claim 4, wherein A is formate,acetate, benzoate, or citrate.
 7. A method according to claim 1, whereinA is nitrate, hydroxide, hexafluorophosphate, sulfate, chlorate, orperchlorate.
 8. A method according to claim 1, wherein the peroxygencompound is activated by a compound that forms a perbenzoic acid, analiphatic peroxocarboxylic acid, or a derivative thereof underperhydrolysis conditions.
 9. A method according to claim 1, wherein theperoxygen compound is an organic per acid, hydrogen peroxide, perborate,percarbonate, or a mixture thereof.
 10. An oxidizing, cleaning, washing,or disinfecting composition comprising 0.0025% to 0.25% by weight of acomplex of the formula (I): [M(NH₃)_(6−x)(L)_(x)]A_(n)  (I) wherein Mis, iron, copper, or ruthenium, L is water, hydroxide, chlorate,perchlorate, (NO₂)⁻, carbonate, hydrogen carbonate, nitrate, acetate, orthiocyanate, x is a number of 0 to 5, A is a salt-forming anion, and nis a number such that complex (I) is has no charge and 0.5% to 50% byweight of a peroxygen compound.
 11. A composition according to claim 10comprising 0.01% to 0.1% by weight of the complex (I).
 12. A compositionaccording to claim 10 comprising 5% to 50% by weight anionic or nonionicsurfactant, up to 60% by weight of a builder, up to 2% by weight of anenzyme, up to 30% by weight of a C₁₋₄ alcohol, a C₂₋₄ diol, an etherderivative of a C₁₋₄ alcohol or a C₂₋₄ diol, or mixtures thereof, and upto 20% by weight of a pH regulator.
 13. A composition according to claim12 comprising 8% to 30% by weight anionic or nonionic surfactant, 5% to40% by weight of a builder, 0.2% to 0.7% by weight of an enzyme, 6% to20% by weight of a C₁₋₄ alcohol, a C₂₋₄ diol, an ether derivative of aC₁₋₄, alcohol or a C₂₋₄ diol, or mixtures thereof, and 1.2% to 17% byweight of a pH regulator.
 14. A composition according to claim 10wherein the peroxygen compound is selected form the group consisting ofhydrogen peroxide, perborate, percarbonate, and mixtures thereof.
 15. Acomposition according to claim 14 comprising 5% to 30% by weight of theperoxygen compound.
 16. The composition of claim 10 comprising 0.5% to40% by weight of the peroxygen compound.
 17. The composition of claim 10comprising 0.5% to 40% by weight of the peroxygen compound.
 18. Thecomposition of claim 10 comprising 5% to 30% by weight of the peroxygencompound.
 19. The composition of claim 10 comprising 5% to 20% by weightof the peroxygen compound.